CN109856038B - Test method for accelerating uniform corrosion of zirconium alloy - Google Patents
Test method for accelerating uniform corrosion of zirconium alloy Download PDFInfo
- Publication number
- CN109856038B CN109856038B CN201910202699.2A CN201910202699A CN109856038B CN 109856038 B CN109856038 B CN 109856038B CN 201910202699 A CN201910202699 A CN 201910202699A CN 109856038 B CN109856038 B CN 109856038B
- Authority
- CN
- China
- Prior art keywords
- test
- corrosion
- group
- weight gain
- gain data
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
The invention discloses a test method for accelerating uniform corrosion of zirconium alloy, which comprises the following steps: step one, setting at least one group of test groups, wherein the test groups comprise a first group, the first group is a plurality of zirconium alloys with the same manufacturing process and the same mark, and corrosion tests are respectively carried out corresponding to different preset temperatures; wherein the test groups are performed prior to the experiment; step two, intermittently measuring the weight gain of the test group to obtain weight gain data, and repeating the step two when the weight gain data is smaller than a preset standard weight gain data; when the weight gain data is more than or equal to the standard weight gain data, terminating the corresponding test group test; step three, repeating the step two until the test of all test groups is terminated; and step four, detecting the corrosion condition of each test group, and acquiring the preset temperature corresponding to the test group with the highest weight gain speed when the corrosion is uniform corrosion. Thus, an accurate uniform corrosion temperature of the zirconium alloy is accelerated, and an effective long-term uniform corrosion acceleration test method is obtained.
Description
Technical Field
The invention relates to the technical field of zirconium alloy uniform corrosion test methods, in particular to a test method for accelerating uniform corrosion of a zirconium alloy.
Background
Zirconium alloys are widely used as cladding materials and core structural materials for water-cooled power reactors. Zirconium alloy corrosion performance is the most important one of the performance of many ex-core applications, and generally, in order to ensure the safe use in the final reactor, zirconium alloy products of various brands and types need to simulate the in-core environment before being formally shaped and stacked, and a long-term steam corrosion test of 400 ℃/10.3MPa for 300 days or longer is carried out.
The experimental period is long, certain challenges are brought to the development and judgment of new products and new processes, and investigation and attempt of accelerated corrosion test conditions are needed to be carried out for shortening the development period.
The feasibility problem of the accelerated corrosion in the zirconium alloy steam environment is not reported in various documents at home. Internationally, only a few scholars have attempted to develop several corrosion test condition studies, such as 400 ℃, 430 ℃ and 500 ℃, based on Zr-4 alloy pipe samples.
However, the test data points are too scattered to give a proper accelerated corrosion test temperature, and an effective long-term uniform corrosion accelerated test method is lacked for zirconium alloy products with other brands and types.
Disclosure of Invention
The invention aims to provide a test method for accelerating uniform corrosion of zirconium alloy, which aims at zirconium alloy products of different grades and types and obtains a set of zirconium alloy uniform corrosion accelerating test method with reproducible appearance and regular multiplying power relationship by systematically comparing the weight gain, the appearance and the thickness of an oxide film of a sample under different periods on the premise of ensuring that a uniform corrosion mechanism is not changed.
In order to solve the problems, the invention provides a test method for accelerating uniform corrosion of a zirconium alloy, which comprises the following steps: step one, setting at least one group of test groups, wherein each test group comprises a first group, the first group is a plurality of zirconium alloys with the same manufacturing process and the same grade, and corrosion tests are respectively carried out corresponding to different preset temperatures; wherein the test groups are performed prior to the experiment; step two, intermittently measuring the weight of the test group to obtain weight data, and repeating the step two when the weight data is smaller than a preset standard weight data; when the weight gain data is greater than or equal to the standard weight gain data, terminating the corresponding test group test; step three, repeating the step two until the test of all test groups is terminated; and step four, detecting the corrosion condition of each test group, and acquiring the preset temperature corresponding to the test group with the highest weight gain speed when the corrosion is uniform corrosion.
Further, the standard weight gain data is weight gain data obtained in a predetermined time when the corrosion test is performed on the test group at the first temperature.
Further, the operation is carried out by adopting acid liquor, and the volume ratio of the acid liquor is 5% hydrofluoric acid: 37% nitric acid: 58% of water; the time is controlled to be 220-240 seconds; and respectively measuring the outer diameters of the samples of the test groups before and after the test groups, and controlling the thickness removal amount of the edge of the outer diameter of the sample to be within the range of 0.01-0.1 mm.
Further, in the first step, the preset temperatures are 410 ℃, 420 ℃ and 427 ℃ respectively.
Further, the corrosion test is a steam uniform corrosion test.
Further, the test equipment used in the corrosion test comprises a high-pressure reaction kettle, and the pressure of the high-pressure reaction kettle is set to be 10.3 MPa.
Furthermore, the test group in the first step also comprises a second group, and the second group is made of zirconium alloy which is different from the first group of test samples in manufacturing process and has the same grade.
Furthermore, the test group in the first step also comprises a third group, and the third group is made of zirconium alloy which has the same manufacturing process and different grades with the first group of test samples.
Further, the first temperature is set to 400 ℃, and the predetermined time is day 300 or day 310.
Further, the zirconium alloy is selected from a pipe, a plate and/or a bar.
The technical scheme of the invention has the following beneficial technical effects:
(1) when other conditions are consistent, the corrosion mechanism of the zirconium alloy product is the same under the environment with the temperature of 420 ℃ and the pressure of 10.3MPa and the environment with the temperature of 400 ℃ and the pressure of 10.3MPa, and the corrosion mechanisms are uniform; the main mechanism of the furuncle-shaped corrosion is that when the temperature is 427 ℃ and the pressure is 10.3 MPa. The same period corrosion weight gain has about 2.4 times of acceleration effect at 420 ℃ compared with 400 ℃, and the appearance can be reproduced. The temperature of 420 ℃ is verified to be the most suitable test condition for accelerating the uniform corrosion of the zirconium alloy.
(2) Although the acceleration effects of corrosion weight increment are different on the premise that the corrosion mechanism of zirconium alloy products of different grades is kept unchanged, tests prove that the corrosion performance judgment period of the zirconium alloy products can be greatly shortened at the temperature of 420 ℃, and further prove that the uniform acceleration zirconium alloy corrosion acceleration test method provided by the embodiment is effective.
Drawings
FIG. 1 is a graph of weight gain comparison trend of Zr-4 alloy pipes provided by the invention under different corrosion conditions;
FIG. 2 is a comparison of the appearance of samples of Zr-4 alloy tubes after different periods of corrosion at 400 deg.C, 420 deg.C and 427 deg.C;
FIG. 3 is a comparison graph of bubble point shapes on the surface of samples of Zr-4 alloy pipes provided by the invention under different corrosion conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Zirconium alloys are an important structural material in nuclear power reactors. Corrosion of zirconium alloy materials is a very significant problem during operation and maintenance of nuclear reactors: on one hand, it affects the normal operation of the reactor, causing unplanned shutdown and huge economic loss; on the other hand, corrosion of the zirconium alloy cladding and corrosion damage of the primary circuit pressure boundary material will cause radioactive leakage, possibly endangering personal safety and even causing serious accidents.
Corrosion of zirconium alloys is generally expressed in terms of oxidation weight gain. Under the condition of certain components and processes, the oxidation weight gain speed of the zirconium alloy product is closely related to the corrosion temperature, and generally, the oxidation weight gain speed is accelerated along with the temperature rise.
410 c is the starting temperature for the homogeneous corrosion test with a significant accelerating effect. The operating experience of nuclear power plants shows that, in addition to homogeneous corrosion of the zirconium alloy cladding, a local corrosion, i.e. a nodular corrosion, also occurs. When the temperature is too high, the corrosion mechanism is changed from a uniform corrosion mechanism to a furuncle-shaped corrosion mechanism, the temperature of 430 ℃ is the critical temperature for changing the uniform corrosion mechanism to the furuncle-shaped corrosion mechanism, and the temperature of 500 ℃ is the temperature of the furuncle-shaped corrosion. The furuncle-shaped corrosion is uneven corrosion, a formed oxide film is loose and easy to fall off, and the early damage and the failure of the cladding can be seriously caused, so the furuncle-shaped corrosion becomes a key factor influencing the service life of the fuel element of the nuclear reactor.
The steps of this embodiment are as follows:
step one, setting at least one group of test groups, wherein each test group comprises a first group, the first group is a plurality of zirconium alloys with the same manufacturing process and the same grade, and corrosion tests are respectively carried out corresponding to different preset temperatures; wherein the test groups were performed prior to the experiment.
Further, a group of experiment groups is arranged, wherein the group comprises a first group, the first group is provided with 30 test samples, the first group of test samples adopts Zr-4 alloy pipes with the outer diameter phi of 9.5mm, the test equipment used for the test comprises a high-pressure reaction kettle, three high-pressure reaction kettles are arranged, the actual +/-3 ℃ temperature difference of the high-pressure reaction kettles is considered, under the condition that the pressure conditions of 10.3MPa in the high-pressure reaction kettles are kept consistent, the preset temperature is sequentially set to be 410 ℃, 420 ℃ and 427 ℃ within the range of 400 plus-minus-plus-pressure 430 ℃, and the corrosion test is carried out in 10 test samples arranged in each reaction kettle. It should be noted that the test sample is treated with the configured acid solution before the test, the acid solution is 5% hydrofluoric acid, 37% nitric acid and 58% water by volume ratio, the time is controlled at 220-.
Step two, intermittently measuring the weight of the test group to obtain weight data, and repeating the step two when the weight data is smaller than a preset standard weight data; when the weight gain data is greater than or equal to the standard weight gain data, terminating the corresponding test group test; step three, repeating the step two until the test of all test groups is terminated;
further, according to the actual test situation, the weight gain of the test sample is measured discontinuously, and it should be noted that the preset standard weight gain adopts: setting 10 Zr-4 alloy pipes with the outer diameter of phi 9.5mm, carrying out uniform corrosion tests for 300 days in a high-pressure reaction kettle pressure with the pressure of 10.3MPa and the temperature of 400 ℃, respectively carrying out corrosion weight gain measurement for 100 days, 200 days and 300 days in the corrosion tests, sequentially recording obtained data, and setting the weight gain data of the 300 th day as preset standard weight gain.
And when the weight gain data is smaller than the preset standard weight gain, the measurement is continuously carried out until the weight gain data is larger than or equal to the preset standard weight gain.
FIG. 1 is a graph of weight gain comparison trend of Zr-4 alloy pipes provided by the invention under different corrosion conditions.
As shown in FIG. 1, weight gain data of the Zr-4 alloy pipe test sample at different corrosion temperatures has small fluctuation, and the change comparison rule is as follows:
the corrosion speed is fastest when the preset temperature is 427 ℃, the weight gain data of a test sample of 30 days is equivalent to the standard weight gain data of 100 days when the temperature is 400 ℃, the weight gain of 220 days when the temperature is 400 ℃ is achieved after 72 days, and the weight gain data of 100 days is slightly higher than the preset standard weight gain data of 300 days when the temperature is 400 ℃. When the preset temperature is 427 ℃, the acceleration of the weight gain data of the test sample in three stages is kept about 3 times of the standard weight gain data.
When the preset temperature is 420 ℃, the corrosion speed is fastest, the weight gain data of a test sample of 42 days is equivalent to the standard weight gain data of 100 days at 400 ℃, the weight gain of 220 days at 400 ℃ is achieved at 96 days, and the weight gain data of 126 days is basically consistent with the preset standard weight gain data of 300 days at 400 ℃. When the preset temperature is 420 ℃, the acceleration of the weight gain data of the test sample in three stages is kept about 2.4 times of the standard weight gain data.
When the preset temperature is 410 ℃, the weight gain data of the test sample of 60 days is equivalent to the standard weight gain data of 100 days at 400 ℃, the weight gain of 220 days at 400 ℃ is achieved at 130 days, and the weight gain data of 180 days is basically consistent with the preset standard weight gain data of 300 days at 400 ℃. When the preset temperature is 420 ℃, the acceleration of the weight gain data of the test sample in three stages is kept about 1.7 times of the standard weight gain data.
The first set of experiments was terminated at 130 days.
And step four, detecting the corrosion condition of each test group, and acquiring the preset temperature corresponding to the test group with the highest weight gain speed when the corrosion is uniform corrosion.
FIG. 2 is a comparison of the appearance of samples of Zr-4 alloy tubes after different periods of corrosion at 400 deg.C, 420 deg.C and 427 deg.C. Since the change in appearance at 410 ℃ is not visually different from that at 400 ℃ in the control group, the 410 ℃ appearance and data comparison can be omitted. Wherein:
(a) appearance at 400 ℃ day 100; (b) appearance at 400 ℃ day 200; (c) appearance at 400 ℃ day 300; (d) appearance at 420 ℃ day 42; (e) appearance at 420 ℃ day 96; (f) appearance at 420 ℃ day 126; (g) the appearance at 427 ℃ on day 30; (h) the appearance at 427 ℃ on day 72; (i) the appearance at 427 ℃ on day 100.
Further, as shown in FIG. 2, at 400 ℃ and 420 ℃ of the Zr-4 alloy pipe sample, the colors of the outer surfaces of the pipes corresponding to different periods are black and bright. When the temperature is increased to 427 ℃ and the corrosion test is carried out for 30 days, the external surface of the comparative sample begins to appear a tiny bubble point similar to a boil corrosion surface at 500 ℃ at 427 ℃. The bubble point size increased continuously by the time the corrosion test was continued for 72 days and 100 days. The actual corrosion mechanism at this temperature is presumed to be mainly a nodular corrosion mechanism.
To accurately determine whether the fine bubble point on the outer surface of the sample at 427 ℃ for 30 days is consistent with the boil-like corrosion bubble point at 500 ℃. Sampling and comparing the two types of microscopic morphologies of the corrosion spots.
FIG. 3 is a comparison graph of bubble point shapes on the surface of samples of Zr-4 alloy pipes provided by the invention under different corrosion conditions. Wherein: (j) spots on day 30 at 427 ℃; (k) spots were obtained at a temperature of 500 ℃ for 8 hours.
As shown in FIG. 3, both spots are prism-shaped, and the ratio of the major axis to the minor axis is close to 1.0, which is completely different from the appearance of the uniform oxide film on the surface of the uniformly corroded zirconium alloy sample.
Thus, the temperature is increased from 400 ℃ to 420 ℃, the zirconium alloy corrosion mechanism is still predominantly homogeneous corrosion, but after a further increase of 7 ℃ to 427 ℃, a nodular corrosion mechanism has played a dominant role therein.
TABLE 1 comparison of oxide film thicknesses of Zr-4 alloy pipe samples under different corrosion conditions
Table 1 lists the oxide film thicknesses of the zirconium alloy samples after different periods of corrosion at 400 deg.C, 420 deg.C and 427 deg.C. Under the temperature of 400 ℃, the thickness of an oxide film on the outer surface of a zirconium alloy sample is gradually increased along with the prolonging of a corrosion period, and the circumferential distribution is uniform; the thickness of the zirconium alloy sample is basically equivalent to the thickness of the zirconium alloy sample oxide film at 400 ℃ and 100 days in a corrosion test at 420 ℃, the thickness of the zirconium alloy sample oxide film is consistent with the thickness of the zirconium alloy sample oxide film at 400 ℃ and 220 days in 96 days, and the corresponding temperature is 400 ℃ and 300 days in 126 days; the oxide film thickness of the zirconium alloy samples was greater for 30 days, 72 days, and 100 days when tested at 427 ℃ for corrosion than for the corresponding zirconium alloys tested at 400 ℃ for 100 days, 220 days, and 300 days.
In conclusion, when the temperature is set to be 427 ℃, the actual corrosion mechanism is mainly a furuncle-shaped corrosion mechanism, and a corrosion test at the temperature of 427 ℃ is eliminated; the preset temperature corresponding to the test group with the highest weight gain speed is 420 ℃, namely the temperature suitable for accelerating the uniform corrosion of the zirconium alloy material is 420 ℃.
In the second embodiment, in order to verify that zirconium alloy products of different manufacturing processes and the same grade are still suitable for the accelerated corrosion test at 420 ℃. A second set of samples was set, using 10 Zr-4 alloy bar products with a diameter of 22mm and 10 Zr-4 alloy sheet products with a thickness of 1mm, and the test procedure was repeated in sequence. The method comprises the steps of arranging two zirconium alloy samples with different manufacturing processes in two corresponding high-pressure reaction kettles, carrying out uniform corrosion tests with preset temperature of 420 ℃ and pressure of 10.3MPa, carrying out weight gain measurement discontinuously, and recording obtained weight gain data sequentially. And comparing the weight gain data with a second preset standard weight gain corresponding to the weight gain data.
Second predetermined standard weight gain: setting 10 Zr-4 alloy bar products with the outer diameter of phi 22mm and 10 Zr-4 alloy plate products with the thickness of 1mm, carrying out uniform corrosion tests for 300 days in a high-pressure reaction kettle pressure with the pressure set to 10.3MPa and the temperature set to 400 ℃, respectively carrying out corrosion weight gain measurement for 100 days, 120 days, 220 days, 250 days and/or 300 days in the corrosion tests, sequentially recording obtained data, and finally respectively setting the weight gain data of the 300 th day as a second preset standard weight gain.
TABLE 2 comparison of corrosion weight gain of Zr-4 alloy bars and sheets under different conditions
As shown in Table 2, when the Zr-4 alloy bar product with the diameter of phi 22mm is adopted, the weight gain data of 42 days is equivalent to the corresponding weight gain data of 400 ℃ and 100 days at the temperature of 420 ℃, the weight gain data of 400 ℃ and 220 days is achieved at 96 days, and the weight gain data after 126 days is basically consistent with the weight gain data of the second standard preset standard with the temperature of 400 ℃ and 300 days. The accelerated corrosion effect of the Zr-4 alloy bar product at the temperature of 420 ℃ is basically consistent with that of the tube, and is about 2.4 times of that of the tube at the temperature of 400 ℃ in the same period;
by adopting a Zr-4 alloy plate product with the thickness of 1mm, when the temperature is 420 ℃, the weight gain data of 60 days is equivalent to the corresponding weight gain data of 120 days at the temperature of 400 ℃, the weight gain data of 250 days at the temperature of 400 ℃ is reached after 126 days, and the weight gain data after 150 days is basically consistent with the weight gain data of the second standard preset standard at the temperature of 400 ℃ for 300 days. The accelerated corrosion effect of the Zr-4 alloy plate at 420 ℃ is basically consistent with that of the tube, but the accelerated corrosion effect is obviously reduced by about 2 times when the temperature is 420 ℃ compared with 400 ℃.
The second set of tests was terminated on day 150.
In conclusion, the temperature suitable for the accelerated corrosion test of the zirconium alloy products with different manufacturing processes and the same grade is still 420 ℃.
In the third embodiment, in order to verify that zirconium alloy products with different grades and the same manufacturing process, i.e., zirconium alloy products with different compositions and proportions, whether the zirconium alloy products are still suitable for the accelerated corrosion test at 420 ℃ is verified. And arranging a third group, wherein 10 Zirlo alloy (phi 9.5 multiplied by 0.57mm) pipes, 10M 5 alloy (phi 9.5 multiplied by 0.57mm) pipes and 10E 110 alloy (phi 9.5 multiplied by 0.57mm) pipes with different brands are adopted as samples of the third group, a uniform corrosion test with the preset temperature of 420 ℃ and the pressure of 10.3MPa is carried out in corresponding three high-pressure reaction kettles, the weight increase is measured discontinuously, and the weight increase data is obtained by recording in sequence. And comparing the weight gain data with third preset standard weight gain data corresponding to the grade.
Third preset standard weight gain: setting 10 Zirlo alloy pipes, 10M 5 alloy pipes and 10E 110 alloy pipes, performing a uniform corrosion test for 300 days in a high-pressure reaction kettle pressure with the pressure set to 10.3MPa and the temperature set to 400 ℃, performing corrosion weight gain measurement for 100 days, 220 days and 310 days of the corrosion test respectively, recording the obtained data in sequence, and finally setting the weight gain data of the 310 th day as a third preset standard weight gain. In order to more accurately obtain the weight gain data and the relationship between the weight gain data and the time, the number of test days is increased by 10 days on the basis of 300 days.
TABLE 3 comparison of corrosion weight gain of zirconium alloy pipes of different grades under different conditions
As shown in Table 3, for Zirlo alloy pipes, the weight gain data of 62 days at the preset temperature of 420 ℃ is equivalent to the weight gain data of 100 days at the temperature of 400 ℃, and the weight gain data of 220 days at the preset temperature of 136 days is basically consistent with the weight gain data of the third standard at the preset temperature of 400 ℃ for 310 days. The accelerated corrosion effect of the Zirlo alloy pipe at 420 ℃ is about 1.6 times of that of the Zirlo alloy pipe at 400 ℃ under the same period.
For the M5 alloy pipe, the weight gain data of 56 days at the preset temperature of 420 ℃ is equivalent to the weight gain data of 100 days at the temperature of 400 ℃, the weight gain data of 220 days at the temperature of 400 ℃ is reached after 123 days, and the weight gain data after 180 days is basically consistent with the third standard weight gain data of 310 days at the temperature of 400 ℃. The accelerated corrosion effect of the M5 alloy pipe at 420 ℃ is about 1.7 times of that of the M5 alloy pipe at 400 ℃ under the same period.
For the E110 alloy pipe, the weight gain data of 56 days at the preset temperature of 420 ℃ is equivalent to the weight gain data of 100 days at the temperature of 400 ℃, the weight gain data of 220 days at the preset temperature of 123 days is achieved, and the weight gain data after 173 days is basically consistent with the third standard weight gain data of 310 days at the preset temperature of 400 ℃. The accelerated corrosion effect of the E110 alloy pipe at 420 ℃ is about 1.8 times of that of the E110 alloy pipe at 400 ℃ under the same period.
The third set of experiments was ended on day 180.
In conclusion, the temperature suitable for the accelerated corrosion test of the zirconium alloy products with different grades is still 420 ℃.
In the fourth embodiment, different from the previous embodiments, 3 experimental groups including the first group, the second group, and the third group are provided. And simultaneously, sequentially performing the first step to the fourth step, wherein in the first step, tests with preset temperatures of 410 ℃, 420 ℃ and 427 ℃ are performed on all the test groups respectively. From the data in the first, second and third examples, the temperature suitable for accelerating the uniform corrosion of the zirconium alloy material is 420 ℃, and the method is suitable for zirconium alloy products of all brands and all manufacturing processes.
The test according to the present embodiment can be performed using a zirconium alloy rod in addition to the zirconium alloy plate and the pipe product according to the above test.
The effect of the present embodiment: the application example shows that when other conditions are consistent, the corrosion mechanisms of the Zr-4 alloy pipe product under the environment with the temperature of 420 ℃ and the pressure of 10.3MPa are the same as those under the environment with the temperature of 400 ℃ and the pressure of 10.3MPa, and are uniform corrosion mechanisms; the main mechanism of the furuncle-shaped corrosion is that when the temperature is 427 ℃ and the pressure is 10.3 MPa. The same period corrosion weight gain has about 2.4 times of acceleration effect at 420 ℃ compared with 400 ℃, and the appearance can be reproduced. Preferably, the accelerated corrosion test conditions of the temperature of 420 ℃ and the pressure of 10.3MPa are also suitable for Zr-4 alloy bar and plate products and other zirconium alloy pipe products (M5, E110, Zirlo alloy and the like) with the only difference of the accelerated effect of corrosion weight gain. The accelerated zirconium alloy uniform corrosion accelerated test method provided by the embodiment can greatly shorten the corrosion performance judgment cycle of various zirconium alloy products on the premise of keeping a corrosion mechanism unchanged, and is suitable for zirconium alloy materials with different manufacturing processes and brands.
The technical scheme of the invention has the following beneficial technical effects:
(1) when other conditions are consistent, the corrosion mechanism of the zirconium alloy product is the same under the environment with the temperature of 420 ℃ and the pressure of 10.3MPa and the environment with the temperature of 400 ℃ and the pressure of 10.3MPa, and the corrosion mechanisms are uniform; the main mechanism of the furuncle-shaped corrosion is that when the temperature is 427 ℃ and the pressure is 10.3 MPa. The same period corrosion weight gain has about 2.4 times of acceleration effect at 420 ℃ compared with 400 ℃, and the appearance can be reproduced. The temperature of 420 ℃ is verified to be the most suitable test condition for accelerating the uniform corrosion of the zirconium alloy.
(2) On the premise of keeping a corrosion mechanism unchanged, zirconium alloy products of different grades have different acceleration effects of corrosion weight increment, but tests prove that the corrosion performance judgment period of the zirconium alloy products can be greatly shortened at the temperature of 420 ℃, and further prove that the uniform acceleration zirconium alloy corrosion acceleration test method provided by the embodiment is effective.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A test method for accelerating uniform corrosion of a zirconium alloy is characterized by comprising the following steps:
step one, setting at least one group of test groups, wherein each test group comprises a first group, the first group is a plurality of zirconium alloys with the same manufacturing process and the same grade, and corrosion tests are respectively carried out corresponding to different preset temperatures; wherein the test group is operated with acid solution before the experiment;
step two, intermittently measuring the weight gain of the test group to obtain weight gain data,
when the weight gain data is smaller than a preset standard weight gain data, repeating the step two,
when the weight gain data is greater than or equal to the standard weight gain data, terminating the corresponding test group test;
step three, repeating the step two until the test of all test groups is terminated;
and step four, detecting the corrosion condition of each test group, and acquiring the preset temperature corresponding to the test group with the highest weight gain speed when the corrosion is uniform corrosion.
2. The test method according to claim 1,
the standard weight gain data is weight gain data acquired at a predetermined time when the corrosion test is performed on the test group at the first temperature.
3. The test method according to claim 1,
the operation is carried out by adopting acid liquor, and the volume ratio of the acid liquor is 5 percent hydrofluoric acid: 37% nitric acid: 58% of water;
the time is controlled to be 220-240 seconds;
and respectively measuring the outer diameters of the samples of the test groups before and after pickling, and controlling the thickness removal amount of the edge of the outer diameter of the sample to be within the range of 0.01-0.1 mm.
4. The test method according to claim 1,
in the first step, the preset temperatures are respectively 410 ℃, 420 ℃ and 427 ℃.
5. The test method according to claim 2,
the corrosion test is a steam uniform corrosion test.
6. The test method according to claim 5,
the test equipment used in the corrosion test comprises a high-pressure reaction kettle, and the pressure of the high-pressure reaction kettle is set to be 10.3 MPa.
7. The test method according to claim 1,
the test group in the first step also comprises a second group, and the second group is made of zirconium alloy which is different from the first group in the manufacturing process and has the same grade as the first group of test samples.
8. The test method according to claim 1,
the test group in the first step also comprises a third group, and the third group is made of zirconium alloy which has the same manufacturing process and different grades with the first group of test samples.
9. The test method according to claim 2, wherein the first temperature is set at 400 ℃ and the predetermined time is at 300 th or 310 th day.
10. The test method according to claim 1, 7 or 8,
the zirconium alloy is selected from a tube, a plate and/or a bar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910064796X | 2019-01-23 | ||
| CN201910064796 | 2019-01-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109856038A CN109856038A (en) | 2019-06-07 |
| CN109856038B true CN109856038B (en) | 2022-01-18 |
Family
ID=66901083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910202699.2A Active CN109856038B (en) | 2019-01-23 | 2019-03-18 | Test method for accelerating uniform corrosion of zirconium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109856038B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5413972A (en) * | 1993-12-23 | 1995-05-09 | The Dow Chemical Company | SiAlON composites and method of preparing the same |
| CN2758751Y (en) * | 2004-12-17 | 2006-02-15 | 中国科学院金属研究所 | Tester for outdoor atmosphere corrosion accelerating |
| CN101497558A (en) * | 2008-02-01 | 2009-08-05 | 浙江龙盛化工研究有限公司 | Method for preparing resorcinol by hydrolyzing m-phenylenediamine |
| CN101566555A (en) * | 2009-04-29 | 2009-10-28 | 中国科学院金属研究所 | High-precision immersed-salt hot corrosion test method |
| CN101701298A (en) * | 2009-10-29 | 2010-05-05 | 国核宝钛锆业股份公司 | Manufacture method of nuclear grade zirconium-niobium alloy cast ingot |
| CN102081034A (en) * | 2010-10-12 | 2011-06-01 | 中国船舶重工集团公司第七二五研究所 | Analog accelerated corrosion test device |
| US8317944B1 (en) * | 2005-09-15 | 2012-11-27 | U.S. Department Of Energy | 9 Cr— 1 Mo steel material for high temperature application |
| CN103276307A (en) * | 2013-04-16 | 2013-09-04 | 宝钢不锈钢有限公司 | High-corrosion resistance high-toughness high-chromium ferrite stainless steel plate and manufacturing method thereof |
| CN104634728A (en) * | 2015-02-09 | 2015-05-20 | 西安热工研究院有限公司 | Evaporator metal corrosion measurement system and method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105699236B (en) * | 2015-12-10 | 2019-06-14 | 新疆警察学院 | The detection method of liquid combustible object in a kind of fire field environment |
| CN106841027A (en) * | 2017-03-02 | 2017-06-13 | 河钢股份有限公司 | The detection of simulation accelerated metal material acidic atmosphere environmental corrosion and evaluation method |
-
2019
- 2019-03-18 CN CN201910202699.2A patent/CN109856038B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5413972A (en) * | 1993-12-23 | 1995-05-09 | The Dow Chemical Company | SiAlON composites and method of preparing the same |
| CN2758751Y (en) * | 2004-12-17 | 2006-02-15 | 中国科学院金属研究所 | Tester for outdoor atmosphere corrosion accelerating |
| US8317944B1 (en) * | 2005-09-15 | 2012-11-27 | U.S. Department Of Energy | 9 Cr— 1 Mo steel material for high temperature application |
| CN101497558A (en) * | 2008-02-01 | 2009-08-05 | 浙江龙盛化工研究有限公司 | Method for preparing resorcinol by hydrolyzing m-phenylenediamine |
| CN101566555A (en) * | 2009-04-29 | 2009-10-28 | 中国科学院金属研究所 | High-precision immersed-salt hot corrosion test method |
| CN101701298A (en) * | 2009-10-29 | 2010-05-05 | 国核宝钛锆业股份公司 | Manufacture method of nuclear grade zirconium-niobium alloy cast ingot |
| CN102081034A (en) * | 2010-10-12 | 2011-06-01 | 中国船舶重工集团公司第七二五研究所 | Analog accelerated corrosion test device |
| CN103276307A (en) * | 2013-04-16 | 2013-09-04 | 宝钢不锈钢有限公司 | High-corrosion resistance high-toughness high-chromium ferrite stainless steel plate and manufacturing method thereof |
| CN104634728A (en) * | 2015-02-09 | 2015-05-20 | 西安热工研究院有限公司 | Evaporator metal corrosion measurement system and method |
Non-Patent Citations (3)
| Title |
|---|
| 304L不锈钢在稀硝酸环境下的腐蚀研究;赵小燕 等;《中国腐蚀与防护学报》;20181031;第38卷(第5期);第455-461页 * |
| High-temperature oxidation of zircaloy-4 in oxygen-nitrogen mixtures;Martin Steinbruck 等;《Oxidation of Metals》;20150721;第85卷;第245-262页 * |
| 镁合金腐蚀行为及机理研究进展;张新 等;《腐蚀科学与防护技术》;20150131;第27卷(第1期);第78-83页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109856038A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Adamson et al. | Irradiation creep and growth of zirconium alloys: A critical review | |
| Sabol et al. | Development of a cladding alloy for high burnup | |
| Baek et al. | Breakaway phenomenon of Zr-based alloys during a high-temperature oxidation | |
| Zhou et al. | Oxidation behavior of matrix graphite and its effect on compressive strength | |
| CN109856038B (en) | Test method for accelerating uniform corrosion of zirconium alloy | |
| CN112730112B (en) | Environment fracture evaluation method suitable for reactor structural component material after long-term service | |
| JPH0233988B2 (en) | ||
| Sanyal et al. | Fracture behavior of thin-walled Zircaloy fuel clad tubes of Indian pressurized heavy water reactor | |
| Majumdar | Designing against low-cycle fatigue at elevated temperature | |
| Bulischeck et al. | Effect of environmental variables on the stress corrosion cracking of Inconel 600 steam generator tubing | |
| Bell et al. | Hydride orientation in Zr-2.5% Nb; how it is affected by stress, temperature and heat treatment | |
| CN104726660A (en) | Forging method for increasing corrosion resistance of 316 LN stainless steel | |
| WO2015047131A1 (en) | Method for the in situ passivation of the steel surfaces of a nuclear reactor | |
| Straalsund et al. | Thermal Densification of Austenitic Stainless Steel | |
| Mao et al. | Creep properties and damage study of Ni-based alloy C276 at high temperature | |
| Xu et al. | Annealing Temperature Effect on Creep Property of CZ Alloy for PWR Modern Fuel Claddings | |
| Kass | Effect of Residual Etchant on the Corrosion Behavior of Zircaloy-2 | |
| Sejnoha et al. | Iodine-induced stress corrosion cracking of fixed deflection stressed slotted rings of Zircaloy fuel cladding | |
| CN114184536B (en) | Analysis method for ferrite thermal aging amplitude modulation decomposition condition | |
| Killeen et al. | Experimental Data on PCI and PCMI within the IFPE Database | |
| Kido et al. | Quantitative assessment of irradiation effect on creep and corrosion properties of Zr-Base alloys | |
| Lee et al. | High Temperature Oxidation Behavior of the Zirconium Alloys in Air and Oxygen | |
| Zuyok et al. | CORROSION RESISTANCE OF THE PRODUCED BY UKRAINIAN ENTERPRISES MAIN STRUCTURAL MATERIALS FOR THE PRIMARY CIRCUIT OF PRESSURIZED WATER REACTORS TO SUBSTANTIATE ITS APPLICATION AND FURTHER LICENSING | |
| Teodoro et al. | Comparison of the mechanical properties and corrosion resistance of zirlo and other zirconium alloys | |
| Riedkina et al. | Investigation into hydride reorientation in dummy fuel rod cladding (Zr-1% Nb) under internal pressure during testing simulating SNF handling and accidents with limiting cladding heating up to 410° С |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |